Brominated vat dyestuffs of the anthanthrone series and process of making same



lc concentrated sulfuric 'acid,sulfur'ic acid monohydrate, fumingsulfuric acid, 'chlorosnl Patented Sept 13, 1932 UmrEof s-rATEs PATENTRICHARD H E, on RANKEoRT-oNrTHE-MAIN, AND WERNER ZERWEO QoEjERANK- oT-oN rHE-1vrArN-F c nErM,IGE ANY, AssIeNoRs T GENERAL -ANILINE WORKS,me, on NEW YORK, N;;Y., A co PoRA'rIoN OF DELAWARE BROMINATED vA'rnYEsTUEEs on THE ANTHANTHRONE SERIESQANDTLPROCESS? 0F No Drawing.OIiginal'appIication filed N 'ovember l, 1526, Serial No. 145,692, andin Germany November;

' 7, 1925. Divided and this application filed December 11, 1929. SerialNo. 4413,319 v This application is a division of. our co-" pendingapplication Serial No..145,697, filed November 1, 1926, which hasmatured into Pat. No.-1,803,757.

anthanthrone in the presence of an inorganic diluent selected fromthegroup consisting of:

fonic acid, sulfuryl chloride, sulfur chlorides, thionyl chloride, The'reactioncan be carried out at ordinary or a elevated temperaturespreferably below 100 C.

As suitable halogenatingagents theremay be used: brominevichlorinetgaswand" solvents of a higher boiling point, easilychlorinating also those compounds ,iivolve, m l ih WWW? r j brilliantgreen color, forming with? alkaline u -W e sulfuryl qm m n P lhydrosulfite violetvcolore'd vats-from which- ClllOIlClG, sulfurClllOI'lClGSffllkall,hyPOQlIlQ-T rites inthe presence of an inorganicacid, and

alkali chlorates in the chloric acid.

According toour newprocess, one or more chlorine atoms maybeintroducedinto the presence of hydroanthanthrone molecule by passing,while stirring, for instance, chlorine into finelygro-und anthanthronein thepresence of an inorganic --d1luent as 'befores'tatedyto whichasmall amount of iodine, ferric chloride, antimony pentachloride,io'dine-trichloride'ora similar compound" may be added asia halogencarrier,

In a similar manner brominemay be .introf duced into the anthanthronemolecule by mixe,

1 about 200 parts of chlorosulfonicacid at ordilnary temperature. Themass is cooled, 0.2, parts of iodine are added and 16 to 20 parts ing"finely powdered anthanthrone' with bro mine 111 the presence of anlnorganlc diluent as before stated, and StlIIlngthQIIllXtllIe for somehours-at ordinary or elevated tempera- H Increase of the weight'showsthat two atoms of' chlorine have enteredinto the molecule. j

tures below 100 C.

a way that approximately two atoms of halogen enter into the molec uljeofthe .anthan- -gg throne.

We have foundthat variable Va dyestufis of the anthanthroneiseries-areobtainable by causing a halogenatlng agent to act'upon' to the generalformula:

Hal stands for chlorine, brominepor ,clilorine+bromine, are when dryyellow to orangeto red powders, difiicultly soluble organic soluble inconcentrated sulfuric acid with a vegetable fibers are dyedyellowish-orange to reddish shades of exceptional brightness and stuifshitherto known.

In order to further illustrate our invention,

being by weight and' alltemperatures in of chlorine are allowed to passin until the The temperature duringthe reaction should preferably notrise above 15 After standing for" some hours,- the mass is poured "onice, and tlieseparated dyest'ulf is filtered and ange vat dyethefollowingexamples are given,- the parts Centigrade degrees, butit isunderstood that our invention is not limited to the particular productsor reaction conditions mentioned" therein: i 1

when exposing dried. The s new dyestufl, thus obtained, having probablythe formula:

I (approximately) is an orange-red powder,; soluble;

in concentrated sulfuric acid with a pure green color. It dyesvegetablefibers from I a violet vat violet shades, turning to a'brilliantyellowish orange of excellent fastness soaping it."

v; z Example? 22 parts of anthanthrone are dissolved in u about 200parts of sulfuric acid monohydrate, 42 parts of fuming sulfuric acid of65% of '1 S0 0.2 parts of iodine and 6 parts of bromine are added andthe solution'is warmed to about 60 for some hours. Then the mass c010r;and dyeing Vegetable fibers from a is cooled down and at ordinarytemperature a current of chlorine is allowed to pass, while cooling,until the increase of the weight shows that one atom of chlorine hasentered into the molecule. The mass is poured on" ice; the

orange-red colored precipitate is filtered,

hus obtained, having prob- :the formula; 3

ClxA-Bry .in '2 formulaX is approximately the number 1, which is when:dry an orange powder, diiricultly soluble in organic-solvents of ahigher boiling point, easily soluble in concentrated sulfuricacid with apure green violet-vat= orange shades of, exceptional brightness andexcellent fastness.

bromineare added and the mass is warmed at s E wample" 3 3. parts i ofanthanthrone are dissolved in about :100 parts of, sulfuric acid of 66B,

then 0.1 .parts of iodineand 3 to 6 parts of about 50 to 100 forsomehours. When the reaction isfinished, the mass is poured on ice,v

the precipitated dyestuff is filtered, washed,"

and any adherent excess of'bromine is removed inthe usual manner whennecessary. -Thenew dyestufi, thus'obtained, is when dry the dyed goodsto the air ora red powder, soluble in concentrated sulfuric acid with apure green color. It forms with alkaline hydro-sulfite a violet vat fromwhich vegetable fibers are dyed the same shades, turning to a brilliantreddish-orange of an excellent fastness by exposing the dyed goods tothe air or by soaplng it.

Ema

.122 of anthanthrone' dissolved in about 200 parts of sulfuric acidmonohydrateif' Then 40 parts of fuming sulfuric acid (containing %,of SO0.2 partsof iodine and 12'parts of bromine are added and the mass iswarmedto' about 60 for some hours, until the bromine is absorbed. Thisfmethodof brominating'is particularly advantageous, because it requiresfor introduc:

*ing one molecule of bromine only one moleitself. In this case oneworks, for'instan'ce, as

follows:

25 parts of- 1.1-dinaphthyI-SS dicar 1 boxylic acid (see UZS.application SerialNo. 118,081, Pat .-No. 1,684,272) are slowlyintroduced into about 200 parts of sulfuricjacidmonohydrate, Care shouldbe taken that the 7 temperature does'not rise much above 60?;

I Thereby, anthanthrone is formed in a quan- I s titative yield. Thenthebromination of the. Y Y formed anthanthroneis ,carried out as 'described above, 1'

We claim: 1. The process which comprises reacting upon anthanthrone withbromine in the pres;

ence of sulfuric acid monohydrate and of a 7 small amount of iodine,with the additionof acid evolved duringthe brominaition is di-' rectlyreoxidized'tobromine and consequently for introducing approximately twoatoms of bromine approximately one molecule of bromine is required, at atemperature of about 60, until approximatelytwo bromine atoms v fumingsulfuric acid so'that the hydrobromic have been introduced into theanthanthrone molecule. i r a I r 7 q 2. The process which comprisesreacting upon 22 parts of anthanthrone dissolved in about 200 parts ofsulfuric acid monohydrate with l2 parts of bromine mixed withabout4:0.partsof fumingmsulfuricacid and 0.2

1 parts of iodine, ata temperature of about 60 until the bromine isabsorbed. I

3. As new compounds, vat dyestufi's corresponding probably to theformula:

tures.

RICHARD HERZ. WERNER ZERWEGK.

